Particles crustal elements

The average particle size distributions for four predominantly crustal elements, Al, Si, Ca, and Ti, are shown in Figure 3. They are essentially identical. It should be pointed out that the downturn of the relative concentrations above 8 ymad (impactor stage 6) is the combined result of the actual distribution of particle sizes in the atmosphere and the efficiency with which these very coarse particles can enter (upward) into the cascade impactor. This efficiency must decrease with increasing particle size and generally depend on inlet design and wind speed. Nevertheless, it is important to note here that the patterns of the four elements are similar, implying a common aerosol source. 

Figure 3. Particle size distributions of crustal elements Al, Si, Ca, and Ti averaged during March 16-19 (for impactor sample numbers indicated, cf. Figure 1) when concentrations were high enough to provide accurate data in the fine fractions.

The results presented a variety of evidence for the identity of Ca sources near our rural sampling site. The distribution of mean crustal element concentrations as a function of wind direction in summer and fall, from the streaker data, suggest a combination of road and soil sources. This agrees with a comparison of crustal abundances in aerosols and source materials. The comparison showed that most of the elements examined had abundances in the aerosol that often fell between those characteristic of roads and soil. This was not the case for Si, but Si may be expected to be less abundant in aerosol samples than in bulk surficial materials because of the preponderance of quartz (Si02) in the larger particles. 

Urban aerosol 105 Three modes nuclei, accumulation, and coarse larger particles contain crustal elements (Fe, Si, etc.), smaller contain nitrate, sulfate, ammonium, and elemental and organic carbon and are formed by combustion processes and gas-to-particle conversion... 

Sulfate particles are usually associated with ammonium occasionally larger particles involving calcium or other crustal elements are found. The acidity of sulfate particles will depend on their source and the extent of contact with ambient ammonia. In the Eastern U.S., the average composition seems to vary between letovicite in the summer [ (NH )3H(S0 )2] and ammonium bisulfate in the fall [NH HSO ] (17). Free H2S0A is found on occasion. 

Shaw and Paur performed FA of all elements observed by XRF in all samples collected at the center site. The data from each quarter were analyzed separately and data for fine and coarse particles were included in the same FAs. For consistency, four factors were used for each quarter. The nature of the factors obtained varied somewhat from quarter to quarter, but three factors emerged consistently (1) fine fraction S and Se, corresponding to our Factor 3 (2) coarse fraction crustal elements, the coarse counterpart of our Factor 2 and (3) fine fraction metals (Fe, Zn, Mn), for which there is no direct analog among the FA of all samples in this work. However, we also performed FA of the samples analyzed from each station. For the center station, Factor 1 was heavily loaded with As, Mn, Sb, Zn, Pb, Br, with smaller loadings of Fe and Se, and the wind trajectories were from more northerly and easterly directions than the average for all samples. Note that a number of the elements on this factor are observable by INAA, but... 

Combustion particles are of complex chemistry, carrying most of the trace elements, toxins or carcinogens generated from the combustion process. Combustion of different types of fuels results in emissions of various trace elements which are present in the fuel material. In most cases there is not just one specific element that is related to the combustion of a particular fuel, but a source profile of elements [2]. For example, motor vehicle emissions contain Br, Ba, Zn, Fe and Pb (in countries where leaded petrol is used) and coal combustion results in the emission of Se, As, Cr, Co, Cu and Al. For comparison, the crustal elements include Mg, Ca, Al, K, Sc, Fe and Mn. Since most of the trace elements are nonvolatile, associated with ultrafine particles and less prone to chemical transformations, they often remain in the air for prolonged periods of time in the form in which they were emitted. 

In Beirut, the elemental composition study of coarse and fine particles showed that crustal elements like Si, Ca, K, Ti, Mn and Fe were prevalent in the coarse fraction while in the fine fraction S, Cu, Zn and Pb predominated. All-time high Ca concentration was due to the abundance of limestone rocks, rich in calcite, in Lebanon, and increased Cl levels correlated with marine air masses. In PM2.5, sulfur concentrations were more prominent in the summer due to the enhancement of photochemical reactions. Sources of sulfur were attributed to local, sea-water and long-range transport from Eastern Europe, with the latter being the most predominate. Anthropogenic elements like Cu and Zn were generated from worn brakes and tires in high traffic density areas. Spikes of Pb were directly linked to... 

This contribution comprehensively reviews the literature reported for particulate emissions of motor vehicles operated under real-world conditions. This article will mainly focus on the results published for size segregated emissions factors of particle mass, elemental and organic carbon, crustal components and selected trace metals, since information is important for health effects studies and source reconciliation modeling efforts. 

Continental aerosol particles contain a significant fraction of minerals. The insoluble fraction consists mainly of the major crustal elements silicon, aluminum and trivalent iron, which occur as alumino-silicates, quartz, and iron oxides. Elements that are eluted from minerals by water are sodium, potassium, calcium (inpart), and magnesium. The water-soluble inorganic salt ftaction is dominated by am-monimn sulfate. Again, sulfate arises from the oxidation of sulfur dioxide, both by gas-phase and by aqueous phase reactions. Whereas the mineral components are mainly found in the coarse particle size range, ammonium sulfate resides mainly in the accumulation mode. Nitrate occurs partly in association with ammoniirm in the accumulation mode, and partly together with sodiirm and other cations in the coarse particle mode. Thus, nitrate often shows a bimodal size distribution. 

Despite the difficulties, there have been many efforts in recent years to evaluate trace metal concentrations in natural systems and to compare trace metal release and transport rates from natural and anthropogenic sources. There is no single parameter that can summarize such comparisons. Frequently, a comparison is made between the composition of atmospheric particles and that of average crustal material to indicate whether certain elements are enriched in the atmospheric particulates. If so, some explanation is sought for the enrichment. Usually, the contribution of seaspray to the enrichment is estimated, and any enrichment unaccounted for is attributed to other natural inputs (volcanoes, low-temperature volatilization processes, etc.) or anthropogenic sources. 

The refined source profiles that best reproduced the coarse fraction are listed in table 7. The calculated profiles of the two crustal components follow those of Mason ( ), though the calcium concentration of 20 in the limestone factor is less than the reported value. The paint pigment profile strongly resembles that calculated for the fine-fraction data. The only major difference is that unlike the fine fraction, the coarse-fraction profile does not associate barium with the paint-pigment factor. The calculated sulfur concentration in the coarse-fraction sulfate factor is much less than that in the fine-fraction and there are sizable concentrations of elements such as aluminum, iron, and lead not found in the fine-fraction profile. The origin of this factor is not clear although as described earlier a possible explanation is that a small part of the sulfate particles in the fine fraction ended up in the coarse samples. 

The use of EF values allows us to set limits on possible sources of elements. In Figure 1, EF values for six cities are compared with the ranges for particles from nine coal-fired power plants. For llthophlle elements such as SI, Tl, Th, K, Mg, Fe and many others not shown, E values are close to unity as expected, as these elements have mainly crustal sources, l.e., entrained soil and the aluminosilicate portion of emissions from coal combustion (see Table I). Many other elements are strongly enriched In some or all cities, and, to account for them, we must find sources whose particles have large values for those elements. Some are fairly obvious from the above discussions Pb from motor vehicles, Na from sea salt In coastal cities, and V and, possibly, N1 from oil In cities where residual oil Is used In large amounts (Boston, Portland, Washington). 

Figure 2 indicates Mn/Fe to be somewhat above the crustal ratio through 19 March, and thereafter a marked Increase is seen. The aerosol ratio Zn/Fe averages about 20 times greater than in the earth crust (somewhat greater on 20-21 March), showing "anomalous" atmospheric enrichment of Zn first recognized by Rahn (7). Since particle size distribution measurements, discussed below, show substantial fine particle concentrations of both Zn and Mn, the processes for their transfer to the atmosphere must be different from those for the other six elements of Figure 2. However, their concentration variations in time still resemble those of Fe shown in Figure 1 and therefore these elements may also be relatively large scale characteristics of air masses, in contrast to S where regional pollution sources and aerosol formation processes must be Important.

Figure 4 presents particle size distributions for six elements which differ among themselves and also from those in Figure 3. Somewhat subjectively, we may identify three patterns in these distributions (a) A coarse mode, typified by Ca and the other elements of Figure 3, which may represent a terrestrial dust origin. This mode can account for coarse particle concentrations observed for Fe, K, Mn, and S. (b) A fine mode with somewhat greater concentrations in the 0.5-1 ymad fraction than in 1-2 ymad particles. The amounts in this <2 ymad range, in excess of those which can be attributed to a coarse crustal aerosol tail with the Ca distribution, show similarities in particle size distributions for Zn, Mn, and possibly Fe. Since the trends shown in Figure 2 point to these elements being characteristic of large scale air masses, their fine modes may be principally due to natural processes.

The composition of fine particles varies from region to region, depending on the precursor emissions. In the northeastern USA, central Europe, and southeastern Asia, more than half of the composition is made up of sulphate particles, due to the combustion of high-sulphur coal and oil. The rest is made up of nitrate particles, carbonaceous material (elemental and organic carbon), and crustal matter (fugitive particles from soil, clay, and rock erosion). 

As reported by Olmez and Gordon (University of Maryland), the concentration pattern of rare earth elements on fine airborne particles (less than 2.5 micrometers in diameter) is distorted from the crustal abundance pattern in areas influenced by emissions from oil-fired plants and refineries. The ratio of lanthanum (La) to samarium (Sm) is often greater than 20 (crustal ratio is less than 6). The unusual pattern apparently results from tlie distribution of rare earths in zeolite catalysts used in refining oil. Oil industry emissions have been found to perturb the rare earth pattern even in very remote locations, such as the Mauna Loa Observatory in Hawaii. 

Particulate emissions data for 21 studies of coal-fired power plants were compiled for use in receptor models. Enrichment factors were calculated (relative to Al) with respect to the earth s crust (EFcrust) and to the input coal (EFcoai). Enrichment factors for input coals relative to crustal material were also calculated. Enrichment factors for some elements that are most useful as tracers of coal emissions (e.g., As, Se) vary by more than ten-fold. The variability can be reduced by considering only the types of plants used in a given area, e.g., plants with electrostatic precipitators (ESPs) burning bituminous coal. For many elements (e.g., S, Se, As, V), EFcrust values are higher for plants with scrubbers than for plants with ESPs. For most lithophiles, EFcrust values are similar for the coarse (>2.5 ym) and fine (<2.5 ym) particle fractions. 

Most previous CMBs, e.g., (10), were performed on whole-filter data sets, for which about half of the mass is from coarse particles. In that case, many elements arise mainly from crustal dust, making them easy to fit. By contrast, the fine fraction contains little crustal material and many elements are highly enriched (relative to crustal abundances) because of passage through combustion processes. Because of the sensitivity of enrichments to details of the combustion sources and their pollution-control devices, these elements are difficult to fit. 

---